Straightforward synthesis of substituted dibenzyl derivatives

Mboyi, Clève D.; Gaillard, Sylvain; Mabaye, Mbaye D.; Pannetier, Nicolas; Renaud, Jean‐Luc

doi:10.1016/j.tet.2013.04.073

Cited by 17 publications

(11 citation statements)

References 64 publications

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“…The σ-aryl ligand of choice was 1-naphthyl (1-Np) because its Ni(II) derivatives are more robust and convenient to work with than the phenyl analogues . Cassar’s catalyst, [(Ph 3 P) 2 Ni(1-Np)Cl], is a particularly easily accessible and versatile, air-stable complex. − The replacement of the Ph ligand in [(PP)Ni(Ph)(CF 3 )] with 1-Np was justified by additional calculations showing that the barriers to the Ar–CF 3 reductive elimination for Ar = 1-Np and Ph are similar, 23.2 vs 22.6 and 27.7 vs 23.2 kcal/mol for PP = dippf and dcypf, respectively. The slightly higher barriers computed for the 1-Np complexes are apparently due to the extra energy cost of the bulkier naphthyl group adopting the proper conformation in the transition state.…”

Section: Experimental Studiesmentioning

confidence: 99%

On the Feasibility of Nickel-Catalyzed Trifluoromethylation of Aryl Halides

et al. 2014

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A computational screening of 42 bidentate phosphines (PP) has yielded promising candidates for Ph–CF3 reductive elimination from Ni(II) complexes of the type [(PP)Ni(Ph)(CF3)]. The computed barriers and synthetic accessibility considerations have identified two PP ligands, dippf and dcypf (ΔG ⧧ = 22.6 and 23.2 kcal/mol, respectively), for experimental studies with 1-Np (1-naphthyl) in place of Ph. Ligand exchange of [(Ph3P)2Ni(1-Np)Cl] with dippf or dcypf has cleanly produced [(dippf)Ni(1-Np)Cl] and [(dcypf)Ni(1-Np)Cl], the first examples of trans square-planar 1,1′-ferrocenediyl backbone-based diphosphine metal complexes devoid of M···Fe dative interactions. Treatment of these chlorides with CF3SiMe3/F–, AgCF3/MeCN or [(Ph3P)3Cu(CF3)] does not furnish isolable or 19F NMR-detectable [(PP)Ni(1-Np)(CF3)] (PP = dippf, dcypf). Other transformations have been observed instead, e.g., ligand exchange with the Ag and Cu complexes, the latter leading to [(dcypf)Cu(CF3)], a rare example of well-defined CF3Cu(I) species. With CF3SiMe3/F–, indirect evidence has been obtained for intermediacy of [(PP)Ni(1-Np)(CF3)] (PP = dippf, dcypf) and instantaneous decomposition via pathways other than C–CF3 reductive elimination. The first Ni(II) complexes with fluoride trans to a non-electron-deficient aryl, [(Cy3P)2Ni(1-Np)F] and [(i-PrXantphos)Ni(1-Np)F], have been prepared and fully characterized. Surprisingly, [(Cy3P)2Ni(1-Np)F] can be produced from [(Cy3P)2Ni(1-Np)Cl] and CsF rather than AgF that is conventionally used for the synthesis of late transition metal fluorides via X/F exchange. While [(Cy3P)2Ni(1-Np)F] is unreactive toward CF3SiMe3, [(i-PrXantphos)Ni(1-Np)F] is readily trifluoromethylated to produce robust [(i-PrXantphos)Ni(1-Np)(CF3)], a rare example of complexes of the type [(PP)Ni(Ar)(CF3)] with PP other than dippe.

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Section: Experimental Studiesmentioning

confidence: 99%

On the Feasibility of Nickel-Catalyzed Trifluoromethylation of Aryl Halides

et al. 2014

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“…Tanaka et al showed that benzyl radicals can also be obtained by the photoinduced cleavage of cobalt(III) complexes, cis-[R 2 Co(bpy) 2 ]-ClO 4 , in the presence of benzyl halides. 21 Other methods for obtaining this conversion include the homocoupling of halides in the presence of various metals 22,23 (Ni, Mg, Mn, Zn, Cu, In, Cr, Fe, Ti), the homocoupling of Grignard compounds, 24 oxidative coupling, 25 Heck cross coupling, 26 the Wittig reaction followed by reduction 27 etc. Though effective, these methods involve expensive reagents and/or ligands, high catalyst loading, environmental hazards, and difficulties in catalyst recycling.…”

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confidence: 99%

An amphiphilic, catalytically active, vitamin B₁₂ derivative

2014

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“…Selective reductive coupling of benzyl bromides to the corresponding 1,2‐diphenylethanes in high yields has been realized by using SmI 2 , vitamin B12, Mn 2 (CO) 10 , Fe(acac) 3 , Cp 2 TiCl, Re(Br)(H)(NO)(PCy 3 ) 2 , NiCl 2 (glyme)/terpyridine, NiCl 2 (PPh 3 ) 2 , RhCl(PPh 3 ) 3 , Co(PMe 3 ) 4 /Me 2 Zn, and NiCl 2 /Sm . However, recyclable heterogeneous catalysis of these two reactions have not been reported in the literature.…”

Section: Resultsmentioning

confidence: 99%

A Highly Stable Porous Viologen Polymer for the Catalysis of Debromination Coupling of Benzyl Bromides with High Recyclability

Tang

Liu

et al. 2019

Asian J Org Chem

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A highly stable porous organic polymer bipy-POP has been prepared from the reaction of 4,4'-bipyridine and tetrakis(4-(bromomethyl)phenyl)methane in N-methylpyrrolidone at 110°C. Bipy-POP exhibited high efficiency in catalyzing the reductive debromination of a variety of benzyl bromides in N,N-dimethylformamide with dithionite as reductive reagent. For substrates that bear electron-donating group(s) on the benzene ring, the reactions selectively afforded dibenzyl sulfone derivatives. Generally, substrates that bear an electron-withdrawing group on the benzene ring gave rise to coupling products ethane derivatives. As exceptions, F, Cl or CF 3 -contained substrates were found to selectively produce sulfone derivatives. The recyclability of bipy-POP for the catalysis of the reaction of (4-fluorophenyl) methyl bromide and diphenylmethyl bromide, which afforded the corresponding sulfone or ethane derivative, revealed that, after 40 times of repeated use, the heterogeneous catalysis did not exhibit important decrease of the activity.[a] J.

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Straightforward synthesis of substituted dibenzyl derivatives

Cited by 17 publications

References 64 publications

On the Feasibility of Nickel-Catalyzed Trifluoromethylation of Aryl Halides

On the Feasibility of Nickel-Catalyzed Trifluoromethylation of Aryl Halides

An amphiphilic, catalytically active, vitamin B₁₂ derivative

A Highly Stable Porous Viologen Polymer for the Catalysis of Debromination Coupling of Benzyl Bromides with High Recyclability

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Straightforward synthesis of substituted dibenzyl derivatives

Cited by 17 publications

References 64 publications

On the Feasibility of Nickel-Catalyzed Trifluoromethylation of Aryl Halides

On the Feasibility of Nickel-Catalyzed Trifluoromethylation of Aryl Halides

An amphiphilic, catalytically active, vitamin B12 derivative

A Highly Stable Porous Viologen Polymer for the Catalysis of Debromination Coupling of Benzyl Bromides with High Recyclability

Contact Info

Product

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An amphiphilic, catalytically active, vitamin B₁₂ derivative